De-Hao Tsai

Protein-silver nanoparticle interactions to colloidal stability in acidic environments.

We report a kinetic study of Ag nanoparticles (AgNPs) under acidic environments (i.e., pH 2.3 to pH ≈7) and systematically investigate the impact of protein interactions [i.e., bovine serum albumin (BSA) as representative] to the colloidal stability of AgNPs. Electrospray-differential mobility analysis (ES-DMA) was used to characterize the particle size distributions and the number concentrations of AgNPs. Transmission electron microscopy was employed orthogonally to provide visualization of AgNPs. For unconjugated AgNPs, the extent of aggregation, or the average particle size, was shown to be increased significantly with an increase of acidity, where a partial coalescence was found between the primary particles of unconjugated AgNP clusters. Aggregation rate constant, kD, was also shown to be proportional to acidity, following a correlation of log(kD) = -1.627(pH)-9.3715. Using ES-DMA, we observe BSA had a strong binding affinity (equilibrium binding constant, ≈ 1.1 × 10(6) L/mol) to the surface of AgNPs, with an estimated maximum molecular surface density of ≈0.012 nm(-2). BSA-functionalized AgNPs exhibited highly-improved colloidal stability compared to the unconjugated AgNPs under acidic environments, where both the acid-induced interfacial dissolution and the particle aggregation became negligible. Results confirm a complex mechanism of colloidal stability of AgNPs: the aggregation process was shown to be dominant, and the formation of BSA corona on AgNPs suppressed both particle aggregation and interfacial dissolution of AgNP samples under acidic environments.

Quantifying nanosheet graphene oxide using electrospray-differential mobility analysis.

We report a high-resolution, traceable method to quantify number concentrations and dimensional properties of nanosheet graphene oxide (N-GO) colloids using electrospray-differential mobility analysis (ES-DMA). Transmission electron microscopy (TEM) was employed orthogonally to provide complementary data and imagery of N-GOs. Results show that the equivalent mobility sizes, size distributions, and number concentrations of N-GOs were able to be successfully measured by ES-DMA. Colloidal stability and filtration efficiency of N-GOs were shown to be effectively characterized based on the change of size distributions and number concentrations. Through the use of an analytical model, the DMA data were able to be converted into lateral size distributions, showing the average lateral size of N-GOs was ∼32 nm with an estimated thickness ∼0.8 nm. This prototype study demonstrates the proof of concept of using ES-DMA to quantitatively characterize N-GOs and provides traceability for applications involving the formulation of N-GOs.

Surface PEGylation of Silver Nanoparticles: Kinetics of Simultaneous Surface Dissolution and Molecular Desorption

A quantitative study of the stability of silver nanoparticles (AgNPs) conjugated with thiolated polyethylene glycol (SH-PEG) was conducted using gas-phase ion-mobility and mass analyses. The extents of aggregation and surface dissolution of AgNPs, as well as the amount of SH-PEG adsorption and desorption, were able to be characterized simultaneously for the kinetic study. The results show that the SH-PEG with a molecular mass of 6 kg/mol (SH-PEG6K) was able to adsorb to the surface of AgNP to form PEG6K-HS-AgNP conjugates, with the maximum surface adsorbate density of ∼0.10 nm(-2). The equilibrium binding constant for SH-PEG6K on AgNPs was calculated as ∼(4.4 ± 0.9) × 10(5) L/mol, suggesting a strong affinity due to thiol bonding to the AgNP surface. The formation of SH-PEG6K corona prevented PEG6K-HS-AgNP conjugates from aggregation under the acidic environment (pH 1.5), but dissolution of core AgNPs occurred following a first-order reaction. The rate constant of Ag dissolution from PEG6K-HS-AgNP was independent of the starting surface packing density of SH-PEG6K on AgNP (σ0), indicating that the interactions of H(+) with core AgNP were not interfered by the presence of SH-PEG6K corona. The surface packing density of SH-PEG6K decreased simultaneously following a first-order reaction, and the desorption rate constant of SH-PEG6K from the conjugates was proportional to σ0. Our work presents the first quantitative study to illustrate the complex mechanism that involves simultaneous aggregation and dissolution of core AgNPs in combination with adsorption and desorption of SH-PEG. This work also provides a prototype method of coupled experimental scheme to quantify the change of particle mass versus the corresponding surface density of functional molecular species on nanoparticles.

Metal–Organic Framework Colloids: Disassembly and Deaggregation

We demonstrate a high-resolution method as an efficient tool to in situ characterize partially reversible assembly and aggregation of metal-organic framework (MOF) colloids. Based on the gas-phase electrophoresis, the primary size and the degree of aggregation of the MOF-525 crystals are tunable by pH adjustment and mobility selection. These findings allow for the further size control of MOF colloids and prove the capability of semiquantitative analysis for the MOF-based platforms in a variety of aqueous formulations (e.g., biomedical applications).

Noble metal-titania hybrid nanoparticle clusters and the interaction to proteins for photo-catalysis in aqueous environments

We report a systematic study of the controlled synthesis of new hybrid spherical TiO2 nanoparticle cluster (TiO2-NPC) homogeneously decorated with noble metal nanoparticles (NPs) by gas-phase evaporation-induced self-assembly. Silver NP (AgNP) was used as the representative noble metal NP. The degradation of methyl blue (MB) in the aqueous solution was chosen as the representative system for the study of photocatalysis, which were tested and evaluated with respect to irradiation conditions and the presence of bovine serum albumin (BSA). The results show that particle size and chemical composition of the hybrid nanostructure were tunable by choosing the suitable concentration of precursors. The photocatalytic activity of AgNP-decorated TiO2-NPC was strongly affected by the light irradiation and the ligand-nanoparticle interfacial interaction. The presence of BSA influenced molecular conjugation to the surface of the hybrid nanostructure. Under conditions of simultaneous competitive adsorption of MB and BSA, the combination of AgNPs improved the photocatalytic activity of the TiO2-NPC-based catalysts. Our work describes a prototype methodology to fabricate TiO2-NPC homogeneously decorated with noble metal NPs with well-controlled material properties. The mechanistic understanding developed in this study can be useful for the future optimization of material properties of hybrid nanostructures versus interfacial interactions with the surrounding molecules.

Thermal Stability of Metal–Organic Frameworks and Encapsulation of CuO Nanocrystals for Highly Active Catalysis

We report an aerosol-based approach to study the thermal stability of metal-organic frameworks (MOFs) for gas-phase synthesis of MOF-based hybrid nanostructures used for highly active catalysis. Temperature-programmed electrospray-differential mobility analysis (TP-ES-DMA) provides the characterization of temperature-dependent morphological change directly in the gas phase, and the results are shown to be highly correlated with the structural thermal stability of MOFs determined by the traditional measurements of porosity and crystallinity. The results show that MOFs underwent thermal decomposition via simultaneous disassembly and deaggregation. Trimeric Cr-based MIL-88B-NH2 exhibited a higher temperature of decomposition ( Td), 350 °C, than trimeric Fe-based MIL-88B-NH2, 250 °C. For UiO-66, a significant decrease of Td by ≈100 °C was observed by using amine-functionalized ligands in the MOF structure. Copper oxide nanocrystals were successfully encapsulated in the UiO-66 crystal (Cu xO@UiO-66) by using a gas-phase evaporation-induced self-assembly approach followed by a suitable thermal treatment below Td (i.e., determined by TP-ES-DMA). Cu xO@UiO-66 demonstrated a very high catalytic activity and stability to CO oxidation, showing at least a 3-time increase in CO conversion compared to the bare CuO nanoparticle samples. The study demonstrates a prototype methodology (1) to determine structural thermal stability of MOFs using a gas-phase electrophoretic method (TP-ES-DMA) and (2) to gas-phase synthesize CuO nanocrystals encapsulated in MOFs.

Gas-phase self-assembly of uniform silica nanostructures decorated and doped with silver nanoparticles

We report a systematic study of the controlled gas-phase synthesis of silver-silica hybrid nanostructures (Ag-SiO2 NP) using the concept of evaporation-induced self-assembly. The approach includes the use of a direct gas-phase electrophoresis for size classification and in situ characterization of mobility size. Transmission electron microscopy and ultraviolet-visible light spectroscopy were employed complementarily to determine the morphology and surface plasmon resonance of Ag-SiO2 NP. Results show that two types of Ag-SiO2 NPs were successfully synthesized: (1) AgNPs decorated on a SiO2-NP (Ag-T-SiO2 NP), and (2) AgNPs doped in a cluster of SiO2-NPs (Ag-C-SiO2 NP). The physical size, morphology, and compositions of Ag-SiO2 NPs were tunable through the adjustments of precursor concentrations and the selected mobility sizes. The results also show that SPR performance, colloidal stability, and dispersibility of AgNPs enhanced significantly in an aqueous environment after the hybridization with SiO2-NP (especially for Ag-C-SiO2 NP). The results and corresponding methodology summarized here provide the proof of concept to fabricate high-purity AgNP-based hybrid nanostructures through gas-phase evaporation-induced self-assembly for future biomedical applications (e.g., hyperthermal therapy, targeted drug delivery, and antibacterial applications).

Aerosol-Based Self-Assembly of a Ag–ZnO Hybrid Nanoparticle Cluster with Mechanistic Understanding for Enhanced Photocatalysis

A gas-phase-controlled synthetic approach is demonstrated to fabricate Ag-ZnO hybrid nanostructure as a high-performance catalyst for photodegradation of water pollutants. The degradation of rhodamine B (RhB) was used as representative, which were tested and evaluated with respect to the environmental pH and the presence of dodecyl sulfate corona on the surface of the catalyst. The results show that a raspberry-structure Ag-ZnO hybrid nanoparticle cluster was successfully synthesized via gas-phase evaporation-induced self-assembly. The photodegradation activity increased significantly (20×) by using the Ag-ZnO hybrid nanoparticle cluster as a catalyst. A surge of catalytic turnover frequency of ZnO nanoparticle cluster (>20×) was observed through the hybridization with silver nanoparticles. The dodecyl sulfate corona increased the photocatalytic activity of the Ag-ZnO hybrid nanoparticle cluster, especially at the acidic and neutral pH environments (maximum 6×), and the enhancement in catalytic activity was attributed to the improved colloidal stability of ZnO-based nanoparticle cluster under the interaction with RhB. Our work provides a generic route of facile synthesis of the Ag-ZnO hybrid nanoparticle cluster with a mechanistic understanding of the interface reaction for enhancing photocatalysis toward the degradation of water pollutants.

Quantitative characterization of colloidal assembly of graphene oxide-silver nanoparticle hybrids using aerosol differential mobility-coupled mass analyses

AbstractIn this work, we develop an aerosol-based, time-resolved ion mobility-coupled mass characterization method to investigate colloidal assembly of graphene oxide (GO)-silver nanoparticle (AgNP) hybrid nanostructure on a quantitative basis. Transmission electron microscopy (TEM) and zeta potential (ZP) analysis were used to provide visual information and elemental-based particle size distributions, respectively. Results clearly show a successful controlled assembly of GO-AgNP by electrostatic-directed heterogeneous aggregation between GO and bovine serum albumin (BSA)-functionalized AgNP under an acidic environment. Additionally, physical size, mass, and conformation (i.e., number of AgNP per nanohybrid) of GO-AgNP were shown to be proportional to the number concentration ratio of AgNP to GO (R) and the selected electrical mobility diameter. An analysis of colloidal stability of GO-AgNP indicates that the stability increased with its absolute ZP, which was dependent on R and environmental pH. The work presented here provides a proof of concept for systematically synthesizing hybrid colloidal nanomaterials through the tuning of surface chemistry in aqueous phase with the ability in quantitative characterization. Graphical AbstractColloidal assembly of graphene oxide-silver nanoparticle hybrids characterized by aerosol differential mobility-coupled mass analyses

Quantifying Surface Area of Nanosheet Graphene Oxide Colloid Using a Gas-Phase Electrostatic Approach

We demonstrate a new, facile gas-phase electrostatic approach to successfully quantify equivalent surface area of graphene oxide (GO) colloid on a number basis. Mobility diameter (dp,m)-based distribution and the corresponding equivalent surface area (SA) of GO colloids (i.e., with different lateral aspect ratios) were able to be identified by electrospray-differential mobility analysis (ES-DMA) coupled to a condensation particle counter (CPC) and an aerosol surface area analyzer (ASAA). A correlation of SA ∝ dp,m2.0 was established using the ES-DMA-CPC/ASAA, which is consistent with the observation by the 2-dimensional image analysis of size-selected GOs. An ultrafast surface area measurement of GO colloid was achieved via a direct coupling of ES with a combination of ASAA and CPC (i.e., measurement time was 2 min per sample; without size classification). The measured equivalent surface area of GO was ∼202 ± 7 m2 g-1, which is comparable to Brunauer-Emmett-Teller (BET) surface area, ∼240 ± 59 m2 g-1. The gas-phase electrostatic approach proposed in this study has the superior advantages of being fast, requiring no elaborate drying process, and requiring only a very small amount of sample (i.e., <0.01 mg). To the best of our knowledge, this is the first study of using an aerosol-based electrostatic coupling technique to obtain the equivalent surface area of graphene oxide on a number basis with a high precision of measurement.